KR20060051015A - Inorganic powder-containing resin composition, transfer film, and process for producing plasma display panel - Google Patents

Abstract

Provided is an inorganic powder-containing resin composition which can preferably form components (for example, dielectric layers, barrier ribs, electrodes, resistors, phosphors, color filters, and black matrices) of a PDP having an excellent pattern shape. It is providing the transfer film and the manufacturing method of PDP which can form the component of PDP which is excellent in workability and excellent in pattern shape.

The present invention contains (a) an inorganic powder, (b) a binder resin, and (c) a low molecular weight compound having an acid value of 30 mgKOH / g or more, and an acid value of 8 to 100 mgKOH measured by the method of JIS K 5601-2-1. It provides the inorganic powder containing resin composition, the transfer film, and the manufacturing method of PDP which are / g.

Inorganic powder-containing resin composition, transfer film, plasma display panel, pattern shape, binder resin, acid value, dielectric layer, partition, electrode, resistor, phosphor, color filter, black matrix

Description

Production method of inorganic powder-containing resin composition, transfer film and plasma display panel {Inorganic Powder-Containing Resin Composition, Transfer Film, And Process for Producing Plasma Display Panel}

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel.

<Brief description of symbols for the main parts of the drawings>

1, 2 glass substrate

3 bulkhead

4 transparent electrodes

5 bus electrode

6 address electrode

7 fluorescent material

8, 9 dielectric layers

10 protective layer

[Patent Document 1] Japanese Unexamined Patent Publication No. Hei 11-162339

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-84833

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-245932

[Patent Document 4] Japanese Patent Application Laid-Open No. 2003-51250

The present invention relates to an inorganic powder-containing resin composition and a transfer film obtained by using the same. Specifically, it is related with the inorganic powder containing resin composition and transfer film which are suitable for formation of the panel material which comprises a plasma display panel.

In recent years, a plasma display attracts attention as a flat fluorescent display. 1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel (hereinafter also referred to as "PDP"). In the figure, (1) and (2) are oppositely arranged glass substrates, (3) are partition walls, and cells are partitioned by the glass substrate 1, glass substrate 2, and partition walls 3. . (4) is a transparent electrode fixed to the glass substrate (1), (5) is a bus electrode formed on the transparent electrode (4) for the purpose of lowering the resistance of the transparent electrode (4), (6) is a glass substrate (2) (7) is a fluorescent material held in the cell, (8) a dielectric layer formed on the surface of the glass substrate (1) to cover the transparent electrode (4) and the bus electrode (5), (9) Denotes a dielectric layer formed on the surface of the glass substrate 2 so as to cover the address electrode 6, and 10 is a protective film made of, for example, magnesium oxide. In addition, in a color PDP, a color filter (red, green, blue), a black matrix, or the like may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

In such a method of manufacturing a PDP dielectric layer, barrier rib, electrode, phosphor, color filter, and black stripe (matrix), a photosensitive inorganic particle-containing resin layer is formed on a substrate, and the film is irradiated with ultraviolet rays through a photomask. The photolithography method is preferably used, in which a pattern is left on a substrate by developing after exposure by exposure to a method such as a scanning method, a method of scanning a laser beam, and drawing directly.

In the photolithography method using an alkaline developer, the pattern shape has been optimized by adjusting the solubility in the developer by adjusting the acid value of the resin. However, it is necessary to add a dispersant having an acidic group in order to satisfy the dispersion stability of the paste, and by the influence of this dispersant, only by adjusting the acid value of the resin, the solubility of the film deviates from an appropriate range and the shape of the pattern obtained This problem arises.

This invention is made | formed based on the above circumstances.

The first object of the present invention is to control the solubility of the inorganic powder-containing resin layer in the developing solution by adjusting the acid value of the inorganic powder-containing resin layer, so that the component of the PDP having excellent pattern shape (for example, dielectric layer, partition, electrode, etc.) And an inorganic powder-containing resin composition capable of preferably forming a resistor, a phosphor, a color filter, and a black matrix).

The 2nd object of this invention is to provide the transfer film which can form the component of PDP which is excellent in workability and excellent in pattern shape.

A third object of the present invention is to provide a method for producing a PDP that can form a component of the PDP that is excellent in workability and excellent in pattern shape.

Another object of the present invention will become apparent from the following description.

The inorganic powder-containing resin composition of the present invention (hereinafter, also simply referred to as "composition of the present invention") is a low molecular compound (hereinafter, referred to as "a) inorganic powder, (b) binder resin, and (c) acid value of 30 mgKOH / g or more (hereinafter, And "acid compound", and the acid value measured by the method of JIS K 5601-2-1 is 8 to 100 mgKOH / g.

The first transfer film of the present invention (hereinafter also referred to as "transfer film I") contains (a) inorganic powder, (b) binder resin, and (c) low molecular weight compound having an acid value of 30 mgKOH / g or more on a supporting film. And it has an inorganic powder containing resin layer whose acid value measured by the method of JISK5601-2-1 is 8-100 mgKOH / g. It is characterized by the above-mentioned.

The second transfer film (hereinafter, also referred to as "transfer film II") of the present invention is a (A) resist layer and (B) (a) inorganic powder, (b) binder resin, and (c) acid value on a supporting film. It is characterized by containing the low molecular weight compound which is 30 mgKOH / g or more, and is formed by laminating the inorganic powder containing resin layer whose acid value measured by the method of JISK5601-2-1 is 8-100 mgKOH / g.

The manufacturing method of the 1st PDP of this invention (henceforth "the manufacturing method I of PDP") forms the layer obtained from the composition of this invention on a board | substrate, forms a resist layer on this layer, and this resist layer After exposing the resist pattern to form a latent image of the resist pattern, the resist layer was developed to present the resist pattern, and the inorganic powder-containing resin layer was etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern. And it forms a panel material which has an inorganic pattern by the method including the process of baking this pattern.

The method for producing a second PDP of the present invention (hereinafter also referred to as "manufacturing method II of PDP") forms a laminated film of a layer and a resist layer obtained from the composition of the present invention on a substrate, and exposes the resist layer by After forming the latent image of the resist pattern, the resist layer is developed to present the resist pattern, and the inorganic powder-containing resin layer is etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern. It is characterized by forming a panel material having an inorganic pattern by a method including a step of firing.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<Inorganic powder containing resin composition>

The composition of the present invention has an acid value of 8 to 100 mgKOH / g, preferably 10 to 95 mgKOH / g, particularly preferably 12 to 90 mgKOH / g, as measured by the method of JIS K 5601-2-1. .

When the value of the acid value of the composition is less than 8 mgKOH / g, there is a tendency that problems such as poor solubility in the etching solution when forming the pattern, deterioration in work throughput due to developing time. In addition, as the developing time becomes longer, the exposed portion swells before the unexposed portion is completely dissolved, and thus the adhesion to the substrate is weakened, and the pattern may be peeled off from the substrate. In addition, when the value of the acid value exceeds 100 mgKOH / g, etching becomes severe from the width of the pattern, the width of the pattern upper surface is narrow, and the width of the pattern bottom surface is widened. As a result, there exists a tendency to generate | occur | produce the problem that the pattern of a favorable shape cannot be obtained.

In addition, the specific measuring method of the acid value in this invention is as follows.

1. An inorganic powder-containing paste is formed into a thin film on a PET film by a bar coater or the like, and the organic solvent is removed by drying the film at 100 ° C. for 5 minutes. (This process becomes unnecessary in the case of transfer film)

2. The predetermined amount of the obtained thin film (in the case of a transfer film, an inorganic powder containing resin layer) is dissolved in 2-butanone.

3. The inorganic powder is allowed to settle by centrifugation, and the supernatant is collected by decantation.

4. After adding phenolphthalein solution, the acid value is calculated | required by titration using 0.1 hydroxide of potassium hydroxide (ethanol solution).

In addition, when manufacturing the transfer film of this invention using the composition of this invention, the acid value of the inorganic powder containing resin layer in this transfer film shows the value which does not change with the acid value of the composition of this invention.

(a) inorganic powder

It does not specifically limit as an inorganic substance which comprises the inorganic powder which comprises the composition of this invention, It can select suitably according to the use (type of component of PDP) of the sintered compact formed with this composition.

Here, about the inorganic powder contained in a composition for forming the "dielectric layer" and "binder" which comprise a PDP, the glass powder which has a softening point in the range of 350-700 degreeC (preferably 400-620 degreeC) is mentioned. have. In the case where the softening point of the glass powder is less than 400 ° C, the glass powder melts in a step in which the organic material is not completely decomposed and removed in the firing step of the film-forming material layer by the composition. A part remains and the partition (glass sintered compact) obtained as a result of this is colored, and light transmittance tends to fall. On the other hand, when the softening point of glass powder exceeds 620 degreeC, since baking needs to be carried out at high temperature rather than 620 degreeC, distortion etc. are easy to generate | occur | produce in a glass substrate. In addition, it is preferable to make the thermal expansion coefficient (alpha 300) of glass powder the same as the thermal expansion coefficient of a base glass substrate. By making the thermal expansion coefficient of a base glass substrate the same as the thermal expansion coefficient of a glass powder, the defects, such as the curvature of a board | substrate and the crack by the distortion between a board | substrate and a pattern at the time of baking, can be avoided. Specifically, the thermal expansion coefficient of the glass powder is preferably 60 × 10 ⁻⁷ to 100 × 10 ⁻⁷ / ° C.

Specific examples of preferred glass powders include I. mixtures of lead oxide, boron oxide and silicon oxide (PbO-B ₂ O ₃ -SiO ₂ system), II. A mixture of zinc oxide, boron oxide and silicon oxide (ZnO-B ₂ O ₃ -SiO _{2 type} ), III. A mixture of lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ system), IV. And a mixture of lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ), and the like.

These glass powders can be contained (combined) in the composition for forming components (for example, an electrode, a resistor, a fluorescent substance, a color filter, and a black matrix) other than a dielectric and a partition. Content of the glass powder in the inorganic powder containing resin composition for obtaining these components is 90 mass% or less normally with respect to inorganic powder whole quantity, Preferably it is 1-90 mass%.

As inorganic powder contained in a composition for forming the "electrode" which comprises a PDP, metal particle containing Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr, etc. is mentioned.

The inorganic powders contained in the composition for forming a "resistor" constituting a PDP, there may be mentioned the particles containing Ru0 ₂ and the like.

The inorganic powders contained in the composition for forming a "fluorescent material" constituting a PDP ^{_{are, Y 2 O 3: Eu 3}} +, Y 2 SiO 5: Eu 3 +, Y 3 Al 5 O 12: Eu 3 +, YVO _{^{4: Eu 3 +, (Y}} , Gd) BO 3: Eu 3 +, Zn 3 (PO 4) 2: a fluorescent material for red, such as Mn; Green fluorescent materials such as Zn ₂ Si0 ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb; _{Y 2 SiO 5: Ce, BaMgAl} 10 O 17: Eu 2 +, BaMgAl 14 O 23: Eu 2+, (Ca, Sr, Ba) 10 (PO 4) 6 Cl 2: Eu 2 +, (Zn, Cd) Particles containing blue fluorescent substances, such as S: Ag, etc. are mentioned.

Examples of the inorganic powder contained in the composition for forming the "color filter" constituting the PDP include a red substance such as Fe ₂ O ₃ and Pb ₃ O ₄ , a green substance such as Cr ₂ O ₃ , and 2 (Al _{2). Na 2 Si 3 O 10) ·} Na 2 may be a particle, or the like material for the blue color, such as s _4.

As inorganic powder contained in a composition for forming the "black matrix (stripe) which comprises a PDP, the particle | grains containing Mn, Fe, Cr, Co, Ni, etc., and these oxides are mentioned.

(b) binder resin

As binder resin which comprises the composition of this invention, the acrylic resin containing a carboxyl group is preferable. Specifically, the copolymer of the following monomer (A) and monomer (C), the monomer (A), the monomer (B), the copolymer of monomer (C), etc. are mentioned.

Monomer (A): Carboxyl group-containing monomers

Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone Mono (meth) acrylates and the like.

Monomer (B): OH-containing monomers

Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; Phenolic hydroxyl group containing monomers, such as o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene.

Monomer (C): Other copolymerizable monomers

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, and glycid (meth) acrylate (Meth) acrylic acid esters other than monomer (a), such as dill and dicyclopentanyl (meth) acrylate; Acrylates having α-hydroxymethyl groups such as methyl-α- (hydroxymethyl) acrylate, ethyl-α- (hydroxymethyl) acrylate and n-butyl-α- (hydroxymethyl) acrylate; Aromatic vinyl monomers such as styrene and α-methylstyrene; Conjugated dienes such as butadiene and isoprene; Macromonomers having polymerizable unsaturated groups such as (meth) acryloyl groups at one end of polymer chains such as polystyrene, methyl poly (meth) acrylate, poly (meth) acrylate, and benzyl poly (meth) acrylate.

The copolymer of the monomer (A) and the monomer (C), or the copolymer of the monomer (A), the monomer (B) and the monomer (C) has alkali solubility due to the presence of a copolymerization component derived from the monomer (A). Will have Especially, the copolymer of a monomer (A), a monomer (B), and a monomer (C) is especially preferable from a viewpoint of the dispersion stability of an inorganic powder, and the solubility to the etching liquid (alkali developing solution) mentioned later.

The content rate of the copolymerization component derived from the monomer (a) in this copolymer becomes like this. Preferably it is 5-60 mass%, Especially preferably, it is 10-40 mass%, The content rate of the copolymerization component derived from a monomer (b) is , Preferably it is 1-50 mass%, Especially preferably, it is 5-30 mass%.

As a particularly preferable composition as carboxyl group-containing resin used for the composition of this invention, methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid n-butyl copolymer, methacrylic acid / succinic acid mono (2- ( (Meth) acryloyloxyethyl) / methacrylic acid 2-hydroxypropyl / methacrylic acid n-butyl copolymer is mentioned.

As molecular weight of the said carboxyl group-containing resin, it is preferable that the weight average molecular weights (Mw) of polystyrene conversion are 5,000-5,000,000, More preferably, it is 10,000-300,000.

Moreover, it is preferable that the glass transition temperature (Tg) of the said carboxyl group-containing resin is -20 degreeC-60 degreeC, More preferably, it is 0 degreeC-50 degreeC. If Tg is 60 degreeC or more, when it is made into a transfer film, the transfer property of a film will deteriorate. Moreover, when Tg is -20 degrees C or less, the adhesiveness of a transfer film will become strong and handleability will fall. In addition, the pattern dissolves during firing, and the linearity of the pattern deteriorates.

It is preferable that the acid value of carboxyl group-containing resin is 100-250 mgKOH / g, More preferably, it is 120-200 mgKOH / g.

Moreover, as content rate of the binder resin in the composition of this invention, it is 1-200 mass parts normally with respect to 100 mass parts of inorganic powder, Preferably it is 5-150 mass parts, Especially preferably, it is 10-125 mass parts. .

(c) acidic compounds

The acid value of the acidic compound which comprises the composition of this invention is 30 mgKOH / g or more, Preferably it is 30-1500 mgKOH / g. In addition, the acid value of an acidic compound is a value of the acid value measured by the method of JISK5601-2-1.

As the acidic compound, an organic acid or an inorganic acid can be used, and an organic acid is preferably used. It is preferable to use fatty acids as organic acid, and it is particularly preferable to use fatty acids having 8 to 30 carbon atoms. Preferable specific examples of the fatty acid include saturated fatty acids such as octanoic acid, undecyl acid, lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid, and arachnic acid; Unsaturated fatty acids, such as elic acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid, are mentioned, These can be used individually or in combination of 2 or more types.

Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, boric acid and phosphoric acid.

Although an acidic compound is normally used as a dispersing agent of an inorganic powder, it may be contained in order to adjust the acid value of a composition.

As a content rate of the acidic compound in the composition of this invention, it is preferable that it is 0.001-15 weight part with respect to 100 weight part of inorganic powder, More preferably, it is 0.01-10 weight part.

(d) plasticizer

It is preferable that the plasticizer is contained in the composition of this invention. When the transfer film is produced by containing a plasticizer, even if the obtained transfer film is bent, minute cracks (cracking and cracking) do not occur on the surface of the inorganic powder-containing resin layer, and the transfer film has excellent flexibility, Winding in a roll shape can also be performed easily.

As a plasticizer used for this invention, the plasticizer containing the compound represented by following formula (1) is preferable. Since the compound is easily decomposed and removed by heat, the organic component does not remain in the structure formed after firing.

Wherein R ¹ and R ⁴ each represent the same or different alkyl group having 1 to 30 carbon atoms, R ² and R ³ each represent the same or different methylene group or an alkylene group having 2 to 30 carbon atoms, and s is 0 to 5 And t is a number from 1 to 10.

In the general formula (1), the alkyl group represented by R ¹ and R ⁴ and the alkylene group represented by R ² and R ³ may be linear or branched, or may be saturated or unsaturated. Carbon number of the alkyl group represented by R <^1> and R <^4> is 1-30, Preferably it is 2-20, More preferably, it is 4-10. When carbon number of this alkyl group exceeds 30, the solubility of the plasticizer with respect to the solvent which comprises this invention may fall, and favorable flexibility may not be obtained. In addition, the value of t becomes like this. Preferably it is 2-6.

Specific examples of the compound represented by the formula (1) include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl di Glycol adipate, and the like.

Moreover, polyfunctional (meth) acrylate can also be used as a plasticizer.

As a specific example of polyfunctional (meth) acrylate, Di (meth) acrylates of alkylene glycol, such as ethylene glycol and propylene glycol; Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypolybutadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone;

Poly (meth) acrylates of trivalent or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol; Poly (meth) acrylates of polyalkylene glycol adducts of trivalent or higher polyhydric alcohols; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediols; Oligos, such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiran resin (meth) acrylate ( And meth) acrylates. These may be used alone or in combination of two or more thereof.

Among them, trimethylolpropane triacrylate and the like are particularly preferably used. It is preferable that it is 100-2,000 as molecular weight of the said polyfunctional (meth) acrylate.

As a content rate of the plasticizer in the composition of this invention, Preferably it is 5-50 mass parts with respect to 100 mass parts of inorganic powder, Especially preferably, it is 10-40 mass parts.

(e) solvent

The composition of the present invention usually contains a solvent in order to impart proper fluidity or plasticity and good film formability. As the solvent used, it is preferable that the affinity with the inorganic powder and the solubility of the binder resin are good, the proper viscosity can be imparted to the composition, and the evaporation can be easily removed by drying.

Moreover, as a especially preferable solvent, ketones, alcohols, and esters (hereinafter, these are referred to as "specific solvent") whose standard boiling point (boiling point at 1 atmosphere) are 100-200 degreeC.

As a specific example of such a specific solvent, Ketones, such as diethyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Saturated aliphatic monocarboxylic acid alkyl esters such as acetic acid-n-butyl and amyl acetate; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate; and the like, and methylbutyl ketone and cyclohexanone can be exemplified. And diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, and the like. These specific solvents can be used individually or in combination of 2 or more types.

Specific examples of solvents other than specific solvents include terebin oil, ethyl cellosolve, methyl cellosolve, terpinol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol, and the like.

As a content rate of the solvent in the inorganic powder containing resin composition of this invention, it can select suitably within the range from which favorable film formation property (fluidity or plasticity) is obtained.

In addition, the composition of the present invention may contain various additives such as a dispersant, a development accelerator, an adhesion aid, an antihalation agent, a leveling agent, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a sensitizer, and a chain transfer agent as optional components.

The composition of the present invention can be prepared by kneading the inorganic powder, the binder resin, the acidic compound and the solvent, and, if necessary, the plasticizer and the optional component using a kneader such as a roll kneader, a mixer, a homo mixer, a ball mill, a bead mill, or the like. Can be.

The composition of the present invention produced as described above is a paste-like composition having fluidity suitable for application, and its viscosity is usually 100 to 1,000,000 cp, preferably 500 to 300,000 cp.

<Transfer film>

The transfer film of the present invention is an inorganic having an acid value of 8 to 100 mgKOH / g, preferably 10 to 95 mgKOH / g, particularly preferably 12 to 90 mgKOH / g, as measured by the method of JIS K 5601-2-1. It is characterized by having a powder containing resin layer. The problem when an acid value is out of the said range is the same as the problem in the inorganic powder containing resin composition of this invention.

The said inorganic powder containing resin layer is normally formed with the composition of this invention. Specifically, about the transfer film I, the composition of this invention is apply | coated on a support film, a coating film is dried, and an inorganic powder containing resin layer is formed. In addition, about the transfer film II, the resist composition mentioned later is apply | coated and dried on a support film, a resist layer is formed, the composition of this invention is apply | coated on this resist layer, and a coating film is dried and an inorganic powder containing resin layer is formed. do.

It is preferable that the support film which comprises a transfer film is a resin film which has heat resistance and solvent resistance, and has flexibility. When a support film has flexibility, a paste composition can be apply | coated by a roll coater, and an inorganic powder containing resin layer can be preserve | saved and supplied in the state wound up to roll shape. As resin which forms a support film, For example, fluorine-containing resin, such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, nylon, cellulose Etc. can be mentioned. The thickness of a support film is 20-100 micrometers, for example.

As a method of apply | coating an inorganic powder containing resin composition, it is necessary to be able to form a thick film thickness (for example, 10 micrometers or more) excellent in the uniformity of film thickness efficiently, and specifically, by a roll coater A coating method, the coating method by a doctor blade, the coating method by a curtain coater, the coating method by a die coater, the coating method by a wire coater, etc. are mentioned as a preferable thing.

Moreover, it is preferable that the mold release process is given to the composition application surface of a support film. Thereby, when forming a PDP component, the peeling operation of a support film can be performed easily.

As drying conditions of a coating film, it is about 0.5 to 30 minutes at 50-150 degreeC, for example, and the residual ratio (content rate in an inorganic powder containing resin layer) of the solvent after drying is usually 2 mass% or less.

The thickness of the inorganic powder-containing resin layer formed on the support film as described above also varies depending on the content, size, and the like of the inorganic powder, but is, for example, 5 to 500 µm. Moreover, as thickness of the resist layer in the transfer film II, it is 0.1-40 micrometers normally, Preferably it is 0.5-20 micrometers.

Moreover, the protective film may be provided in the surface of an inorganic powder containing resin layer, and a polyethylene film, a polyvinyl alcohol-type film, etc. are mentioned as this protective film.

<Production method of PDP>

The production method I of the PDP of the present invention comprises (i) forming an inorganic powder-containing resin layer on a substrate using the composition of the present invention or the transfer film of the present invention, (ii) forming a resist layer on the layer, ( iii) exposing the resist layer to form a latent image of the resist pattern, and then (iv) developing the resist layer to present the resist pattern, and (v) etching the inorganic powder-containing resin layer onto the resist pattern. A pattern of a corresponding inorganic powder-containing resin layer is formed, and (vi) a panel material having an inorganic pattern is formed by a method including a step of baking the pattern. Below, each process is demonstrated.

(i) Formation process of inorganic powder containing resin layer

An inorganic powder containing resin layer can be formed by apply | coating the composition of this invention on a board | substrate, or transferring the inorganic powder containing resin layer in the said transfer film on a board | substrate using the transfer film of this invention. According to the method using a transfer film, the inorganic powder containing resin layer excellent in film thickness uniformity can be formed easily, and the film thickness uniformity of the pattern formed can be aimed at. Moreover, by repeating n times transfer using the said transfer film, you may form the laminated body which has an inorganic powder containing resin layer of n layer (n represents the integer of 2 or more). Moreover, the said laminated body can also be formed by carrying out the collective transfer of the laminated body containing n-layered inorganic powder containing resin layer on a board | substrate using the transfer film formed on the support film.

As a coating method of the composition of this invention, various methods, such as the screen printing method, the roll coating method, the rotation coating method, the flexible coating method, are mentioned, and after apply | coating the composition of this invention, by the method of drying a coating film An inorganic powder containing resin layer can be formed. In addition, an n-layer laminate can be formed by repeating the above steps n times.

Moreover, when an example of the transfer process using a transfer film is shown, it is as follows. After peeling the protective film layer of the transfer film used as needed, the transfer film is superposed so that the surface of an inorganic powder containing resin layer may contact a board | substrate surface, and this inorganic transfer film is thermocompressed with a heating roller, etc. The support film is peeled off from the containing resin layer. As a result, the inorganic powder-containing resin layer is transferred to and adhered to the surface of the substrate. Here, as transfer conditions, the surface temperature of a heating roller can show 40-140 degreeC, the roll pressure by a heating roller is 0.1-10 kg / cm, and the moving speed of a heating roller is 0.1-10 m / min, for example. In addition, the board | substrate may be preheated and can be 40-140 degreeC as preheating temperature, for example.

(ii) formation process of resist layer

A resist layer is formed on the surface of the formed inorganic powder containing resin layer. As a resist which comprises this resist layer, any of a positive resist and a negative resist may be sufficient.

The resist layer can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a rotation coating method, a flexible coating method, and then drying the coating film.

Moreover, it can also form by transferring the resist layer formed on the support film to the surface of an inorganic powder containing resin layer. According to such a formation method, the process improvement (high efficiency) in the formation process of a resist layer can be aimed at, and the film thickness uniformity of the inorganic powder pattern formed can be aimed at.

As a film thickness of a resist layer, it is 0.1-40 micrometers normally, Preferably it is 0.5-20 micrometers.

(iii) exposure process of resist layer

The latent image of a resist pattern is formed by the method of performing selective irradiation (exposure) of radiation, such as an ultraviolet-ray, a method of scanning a laser beam, etc. through the exposure mask on the surface of a resist layer. As the radiation irradiation apparatus, although an ultraviolet irradiation apparatus, a semiconductor apparatus and an exposure apparatus used when manufacturing a semiconductor and a liquid crystal display device generally used in the port lithography method are used, it is not specifically limited.

In addition, when the resist layer is formed by transfer, it is preferable to perform exposure in a state in which the supporting film coated on the resist layer is not peeled off.

(vi) development process of resist layer

By developing the exposed resist layer, the resist pattern (latent image) is made to present. Here, as the development treatment conditions, the type, composition, and concentration of the developing solution, the developing time, the developing temperature, the developing method (for example, the dipping method, the shaking method, the shower method, the spray method, the paddle method), and the developing device, depending on the type of the resist layer or the like. Etc. can be selected as appropriate.

By this developing step, a resist pattern (pattern corresponding to the mask for exposure) formed of the resist remaining portion and the resist removing portion is formed.

This resist pattern acts as an etching mask in a subsequent step (etching step), and the constituent material (photocured resist) of the resist remaining portion needs to have a smaller dissolution rate in the etching solution than the constituent material of the inorganic powder-containing resin layer. have.

(v) Etching Step of Inorganic Powder-Containing Resin Layer

In this step, the inorganic powder-containing resin layer is etched to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern.

That is, the part corresponding to the resist removal part of a resist pattern among the inorganic powder containing resin layers melt | dissolves in an etching liquid, and is selectively removed, and the glass substrate surface is exposed in the part corresponding to the resist removal part in an inorganic powder containing resin layer. . As a result, an inorganic powder-containing resin layer pattern composed of the resin layer remaining portion and the resin layer removing portion is formed.

Here, as the etching treatment conditions, the type, composition, and concentration of the etching liquid, the treatment time, the treatment temperature, and the treatment method (for example, the dipping method, the shaking method, the shower method, the spray method, and the paddle method) depending on the type of the inorganic powder-containing resin layer and the like. , A processing apparatus or the like can be selected as appropriate.

In addition, by selecting the type of the resist layer and the inorganic powder-containing resin layer so that the same solution as that used in the developing step can be used as the etching solution, the developing step and the etching step can be carried out continuously, and the production is simplified by the process. The efficiency can be improved.

Here, it is preferable that the resist residual part which comprises a resist pattern is melt | dissolved gradually at the time of an etching process, and is completely removed at the stage (at the end of an etching process) in which the inorganic powder containing resin layer pattern was formed.

In addition, even if some or all of the resist remaining portion remains after the etching treatment, the resist remaining portion is removed in the next baking step.

(vi) firing process

The pattern of the inorganic powder-containing resin layer is calcined to dissipate the organic substance at the remaining portion of the inorganic powder-containing resin layer. By this step, organic substances are lost from the pattern of the inorganic powder-containing resin layer to form inorganic layers such as glass layers, metal layers, and phosphor layers, and dielectric layers, partition walls, electrodes, resistors, phosphors, color filters, black matrices, and the like. PDP components are formed.

Here, as the temperature of the baking treatment, it is necessary to be a temperature at which the organic substance disappears in the inorganic powder-containing resin layer (residual portion), and is usually 400 to 600 ° C. In addition, baking time is 10 to 90 minutes normally.

In the manufacturing method II of PDP, it has the same process as the manufacturing method I of PDP except having formed the laminated film of an inorganic powder containing resin layer and a resist layer collectively on a board | substrate. The laminated film is preferably formed by transfer using the transfer film II of the present invention.

An example of the transfer process is as follows. After peeling the protective film layer of the transfer film II used as needed, the transfer film II was superposed so that the surface of an inorganic powder containing resin layer might contact the surface of a board | substrate, and this transfer film II was thermocompression-bonded by the heating roller etc. Thereafter, the support film is peeled off from the resist layer surface of the laminated film. Thereby, the laminated film of a resist layer and an inorganic powder containing resin layer is transcribe | transferred on the surface of a board | substrate, and it will be in the state in which it adhered. Here, as transfer conditions, the surface temperature of a heating roller can show 40-140 degreeC, the roll pressure by a heating roller is 0.1-10 kg / cm, and the moving speed of a heating roller is 0.1-10 m / min, for example. In addition, the board | substrate may be preheated and can be 40-140 degreeC as preheating temperature, for example.

Hereinafter, the material used for each said process, various conditions, etc. are demonstrated.

<Resist layer (resist composition)>

As a resist composition used in order to form a resist layer, (1) alkali developing radiation sensitive resist composition, (2) organic solvent developing radiation sensitive resist composition, (3) aqueous developing radiation sensitive resist composition, etc. Although it can be illustrated, as mentioned above, since it is preferable to make the developing solution used for image development of a resist layer and the etching solution used for the etching process of an inorganic powder containing resin layer into the same solution, as a resist composition, it is (1) alkali It is preferable to use a developing radiation-sensitive resist composition.

Hereinafter, these resist compositions are demonstrated.

(1) alkali developing radiation sensitive resist composition

An alkali developing radiation sensitive resist composition contains alkali-soluble resin and a radiation sensitive component as an essential component.

As alkali-soluble resin which comprises an alkali image development type radiation sensitive resist composition, alkali-soluble resin illustrated as what comprises the binder resin component of an inorganic powder containing resin composition is mentioned.

As a radiation sensitive component which comprises an alkali-developing radiation-sensitive resist composition, For example, (A) The combination of a polyfunctional monomer and a photoinitiator, (B) A photo-acid generator which forms an acid by melamine resin and irradiation. The combination of and the like can be exemplified as a preferable one, and a combination of a polyfunctional (meth) acrylate and a photopolymerization initiator is particularly preferable among the combinations of (a) above.

As a specific example of the polyfunctional (meth) acrylate which comprises a radiation sensitive component, Di (meth) acrylates of alkylene glycols, such as ethylene glycol and propylene glycol; Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypolybutadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone;

Poly (meth) acrylates of trivalent or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, dipentaerythritol, etc .; Poly (meth) acrylates of polyalkylene glycol adducts of trivalent or higher polyhydric alcohols; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediols; Oligos, such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiran resin (meth) acrylate ( And meth) acrylates. These may be used alone or in combination of two or more thereof.

Moreover, as a specific example of the photoinitiator which comprises a radiation sensitive component, benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy Cyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 '-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2- Carbonyl compounds such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Azo compounds or azide compounds such as azoisobutyronitrile and 4-azide benzaldehyde; Organic sulfur compounds such as mercaptan disulfide; Organic peroxides such as benzoyl peroxide, di-tret-butyl peroxide, tret-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide; 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] -4,6-bis Trihalo methanes such as (trichloromethyl) -1,3,5-triazine; Imidazole dimers such as 2,2'-bis (2-chlorophenyl), 4,5,4 ', 5'-tetraphenyl and 1,2'-biimidazole; It can be used in combination of 2 or more type.

As a content rate of the radiation sensitive component in this alkali developing radiation sensitive resist composition, it is 1-300 weight part normally per 100 weight part of alkali-soluble resin, Preferably it is 10-200 weight part.

Moreover, about an alkali developing radiation sensitive resist composition, in order to provide favorable film formation property, the appropriate organic solvent is contained. As such an organic solvent, the solvent illustrated as what comprises an inorganic powder containing resin composition is mentioned.

(2) Organic solvent developing radiation sensitive resist composition:

The organic solvent developing type radiation sensitive resist composition contains at least one selected from natural rubber, synthetic rubber, cyclized rubber in which these are cyclized, and an azide compound as essential components.

As a specific example of the azide compound which comprises the organic-solvent development type radiation sensitive resist composition, 4,4'- diazide benzophenone, 4,4'- diazide diphenylmethane, 4,4'- diazide steel Ben, 4,4'-diazidechalcon, 4,4'-diazidebenzalacetone, 2,6-di (4'-azidebenzal) cyclohexanone, 2,6-di (4'-azidebenzal ) -4-methylcyclohexanone etc. can be mentioned, These can be used individually or in combination of 2 or more types.

Moreover, in order to provide favorable film formation property, the organic solvent developing type radiation sensitive resist composition contains an organic solvent normally. As such an organic solvent, the solvent illustrated as what comprises an inorganic powder containing resin composition is mentioned.

(3) aqueous developing radiation-sensitive resist composition:

The aqueous developing radiation-sensitive resist composition contains, for example, a water-soluble resin such as polyvinyl alcohol and at least one selected from diazonium compounds and dichromic acid compounds as essential components.

The resist composition used in the production method of the present invention may contain various additives such as development accelerators, adhesion aids, anti-halation agents, storage stabilizers, antifoaming agents, antioxidants, ultraviolet absorbers, fillers, phosphors, pigments, and dyes as optional components. Can be.

<Substrate>

As a board | substrate material, the plate-shaped member containing insulating materials, such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide, is mentioned, for example. About the surface of this plate-shaped member, Chemical treatment with a silane coupling agent etc. as needed; Plasma treatment; Appropriate pretreatment such as thin film formation treatment by ion plating method, sputtering method, vapor phase reaction method, vacuum deposition method or the like can be performed.

Moreover, in this invention, it is preferable to use glass which has heat resistance as a board | substrate. As a glass substrate, Asahi Glass Co., Ltd. product PD200 is mentioned as a preferable thing, for example.

<Exposure mask>

As an exposure pattern of the mask for exposure used in the exposure process by the manufacturing method of this invention, although it changes with materials, a stripe form and a lattice form are generally used. The width of the stripe or lattice is, for example, 10 to 500 mu m.

<Development amount>

As a developing solution used at the developing process of a resist layer, it can select suitably according to the kind of resist layer (resist composition). Specifically, an alkaline developer can be used for the resist layer of the alkali developing radiation-sensitive resist composition, an organic solvent developer can be used for the resist layer of the organic solvent-type radiation-sensitive resist composition, and an aqueous developing radiation-sensitive An aqueous developer can be used for the resist layer by the resist composition. In this invention, since an alkali developing radiation sensitive resist composition is used preferably, alkaline developing solution can be used preferably.

As an active ingredient of alkaline developing solution, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, for example Inorganic alkaline compounds such as lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate and ammonia; Tetramethylammonium Hydroxide, Trimethylhydroxyethylammonium Hydroxide, Monomethylamine, Dimethylamine, Trimethylamine, Monoethylamine, Diethylamine, Triethylamine, Monoisopropylamine, Diisopropylamine, Ethanolamine Organic alkaline compounds, such as these, etc. are mentioned.

An alkaline developing solution can be manufactured by dissolving 1 type, or 2 or more types of the said alkaline compound in water etc. The concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass. In addition, after the image development process by alkaline developing solution is performed, the water washing process is normally performed.

As a specific example of the organic solvent developing solution, organic solvents, such as toluene, xylene, and butyl acetate, are mentioned, These can be used individually or in combination of 2 or more types. In addition, after the development process by the organic solvent developing solution is performed, the rinse process by a poor solvent is performed as needed.

Specific examples of the aqueous developer include water and alcohols.

<Etching liquid>

It is preferable that the etching liquid used at the etching process of an inorganic powder containing resin layer is an alkaline solution. Thereby, alkali-soluble resin contained in an inorganic powder containing resin layer can be easily dissolved and removed.

In addition, since the inorganic powder contained in the inorganic powder-containing resin layer is uniformly dispersed by the alkali-soluble resin, the inorganic powder is also removed simultaneously by dissolving and washing the alkali-soluble resin which is the binder resin in the alkaline solution.

As an alkaline solution used as an etching solution here, the solution of the same composition as a developing solution is mentioned.

And when an etching liquid is the same solution as the alkaline developing solution used at a developing process, it becomes possible to perform a developing process and an etching process continuously, and the manufacturing efficiency can be improved by simplifying a process.

In addition, after the etching process by alkaline solution is performed, a water washing process is performed normally.

Moreover, as an etching liquid, the organic solvent which can melt | dissolve the binder resin of an inorganic powder containing resin layer can also be used. As such an organic solvent, the solvent illustrated as what comprises an inorganic powder containing resin composition is mentioned.

In addition, after the etching process with an organic solvent is performed, the rinse process with a poor solvent is performed as needed.

<Example>

Hereinafter, although the Example of this invention is described, this invention is not limited by these. In addition, "part" represents a "mass part" below.

In addition, Mw is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) (brand name HLC-802A) by the Tosoh Corporation.

<Example 1>

(1) Preparation of Inorganic Powder-Containing Resin Composition

(a) 100 parts of Ag powder (average particle diameter: 2.2 µm) and glass frit (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system, average particle diameter of 3 µm, amorphous form, softening point 520 ° C, thermal expansion coefficient α ³⁰⁰ as inorganic powder = 87 × 10 ⁻⁷ / ° C.) 10 parts, (b) methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid-n-butyl / succinic acid mono (2- (meth) acrylic acid Iloxyethyl) = 15/25/40/20 (mass%) copolymer (Mw = 50,000) 60 parts, (c) 3 parts of oleic acid as an acidic compound, (d) 20 parts of trimethylolpropane triacrylates as a plasticizer And (e) 100 parts of propylene glycol monomethyl ether as a solvent were kneaded with a bead mill and then filtered with a stainless mesh (500 mesh, 25 µm diameter) to prepare the inorganic powder-containing resin composition I of the present invention.

(2) Measurement of Acid Value of Inorganic Powder-Containing Resin Composition I

An inorganic powder-containing resin composition I was formed in a thin film form on a pet film using a bar coater, and the formed thin film was dried in a clean oven at 100 ° C. for 5 minutes to form an inorganic powder-containing resin layer from which an organic solvent was removed. 1.1045 g of the inorganic powder-containing resin layer from which the organic solvent was removed was weighed and dissolved in 100 ml of 2-butanone. After confirming complete dissolution, the inorganic powder was precipitated by centrifugation, and the supernatant was fractionated by decantation. Phenolphthalein was added to the supernatant, and titrated using 0.1 N potassium hydroxide (ethanol solution). The acid value was calculated from the titration amount and found to be 24.5 mgKOH / g.

(3) Formation of Inorganic Powder-Containing Resin Layer

After apply | coating inorganic powder containing resin composition I to thickness 10micrometer on the glass substrate by screen printing, it dried for 5 minutes in the clean oven at 100 degreeC, and formed the inorganic powder containing resin layer.

(4) Formation of Resist Layer

60 parts of cyclohexyl methacrylate / methacrylic acid = 85/15 (mass%) copolymer (Mw = 50,000), 40 parts of heptapropylene glycol diacrylate, 2-benzyl-2-dimethylamino-1- (4- 5 parts of morpholinophenyl) -butan-1-one and 250 parts of cyclohexanone were kneaded to prepare a resist composition, and the resist composition was applied onto the inorganic powder-containing resin layer by screen printing at a film thickness of 10 탆. 5 minutes in a clean oven at 100 ° C. to form a resist layer.

(5) Exposure process of resist layer

The g-line (436 nm) and h-rays were made by ultra-high pressure mercury lamp through the mask for exposure of stripe negatives with a line width of 100 micrometers, and a space width of 400 micrometers with respect to the laminated film of the inorganic powder containing resin layer and the resist layer formed on the glass substrate. (405 nm) and i-rays (365 nm) were mixed. The exposure amount at this time was 400 mJ / cm 2 in terms of illuminance measured by a 365 nm sensor.

(6) developing and etching process

The developing process for the exposed resist layer and the etching process for the inorganic powder-containing resin layer were continuously performed for 120 seconds by a shower method using a 0.3 mass% sodium carbonate aqueous solution having a solution temperature of 30 ° C., followed by ultrapure water. It washed with water using. As a result, the uncured resist layer not irradiated with ultraviolet rays was removed to present the resist pattern, and the portion corresponding to the resist removing portion of the resist pattern was subsequently removed to form a pattern of the inorganic powder-containing resin layer. .

(7) firing process

The glass substrate in which the pattern of the inorganic powder containing resin layer was formed was baked in the baking furnace for 30 minutes in 590 degreeC temperature atmosphere. Thereby, the panel material by which the electrode of pattern width 100 micrometers and thickness 6 micrometers is formed on the surface of a glass substrate was obtained. The obtained electrode was excellent in pattern shape and uniformity of shape, and crack was not recognized.

<Example 2>

(1) Preparation of Inorganic Powder-Containing Resin Composition

(a) Co ₃ O ₄ as inorganic powder 100 parts of powder (average particle diameter 0.4 µm) and glass frit (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system, average particle diameter 3 µm, indeterminate, softening point 520 ℃, coefficient of thermal expansion α ³⁰⁰ = 87 × 10 ^-7 / (C) 10 parts, (b) methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid-n-butyl / succinic acid mono (2- (meth) acryloyloxyethyl) = 15 / 60 parts of 25/40/20 (mass%) copolymer (Mw = 50,000), (c) 1.5 parts of oleic acid as an acidic compound, (d) 20 parts of trimethylolpropane triacrylate as a plasticizer, and (e) solvent 100 parts of propylene glycol monomethyl ether as (g) and 10 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one as a photopolymerization initiator with a bead mill, followed by stainless steel mesh The inorganic powder containing resin composition II of this invention was manufactured by filtering by (500 mesh, 25 micrometer diameter).

(2) Measurement of Acid Value of Inorganic Powder-Containing Resin Composition II

An inorganic powder-containing resin composition was formed in a thin film form on a pet film using a bar coater, and the formed thin film was dried in a clean oven at 100 ° C. for 5 minutes to form an inorganic powder-containing resin layer from which an organic solvent was removed. 1.1045 g of the inorganic powder-containing resin layer from which the organic solvent was removed was weighed and dissolved in 100 ml of 2-butanone. After confirming complete dissolution, the inorganic powder was precipitated by centrifugation, and the supernatant was fractionated by decantation. Phenolphthalein was added to the supernatant, followed by titration using 0.1 ml of calcium hydroxide (ethanol solution). The acid value was calculated from the titration amount and found to be 22.4 mgKOH / g.

(3) Formation of Inorganic Powder-Containing Resin Layer

After apply | coating inorganic powder containing resin composition II on the glass substrate by screen printing at thickness of 10 micrometers, it dried for 5 minutes in 100 degreeC clean oven, and formed the inorganic powder containing resin layer.

(4) Exposure process of inorganic powder containing resin layer

With respect to the inorganic powder-containing resin layer formed on the glass substrate, g-line (436 nm), h-line (405 nm), and ultra-high pressure mercury lamps were interposed through a stripe negative exposure mask having a line width of 100 µm and a space width of 400 µm. The mixed light of i line | wire (365 nm) was irradiated. The exposure amount at this time was 400 mJ / cm 2 in terms of illuminance measured by a 365 nm sensor.

(5) developing process

The developing treatment for the inorganic powder-containing resin layer subjected to the exposure treatment was continuously performed for 70 seconds by a shower method using a 0.3 mass% sodium carbonate aqueous solution having a solution temperature of 30 ° C, followed by washing with ultrapure water. Thereby, the pattern of the inorganic powder containing resin layer was formed by removing the uncured inorganic powder containing resin layer to which the ultraviolet-ray was not irradiated.

(6) firing process

The glass substrate in which the pattern of the inorganic powder containing resin layer was formed was baked in the baking furnace for 30 minutes in 590 degreeC temperature atmosphere. Thereby, the panel material in which the black stripe of pattern width 100 micrometers and thickness 6 micrometers is formed on the surface of a glass substrate was obtained. The obtained electrode was excellent in pattern shape and uniformity of shape, and crack was not recognized.

<Example 3>

(1) Preparation of Resist Composition:

Benzyl methacrylate / methacrylic acid = 75/25 (wt%) copolymer (Mw = 30,000) as a binder polymer, 60 parts of tripropylene glycol diacrylates as a polyfunctional monomer, 2- (4- as a photoinitiator After kneading methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and 100 parts of propylene glycol monomethyl ether acetate as a solvent, a cartridge filter (2 탆 diameter) was kneaded. By filtering with an alkali developing radiation-sensitive resist composition (hereinafter referred to as "resist composition") was prepared.

(2) Preparation of the transfer film:

By the following operations (a) to (c), a transfer film for forming an electrode of the present invention, in which a laminated film formed by sequentially laminating a resist film and an inorganic powder-containing resin layer is formed on a support film.

(A) The resist composition prepared in the above (3) was applied onto a support film I made of a PET film having a film thickness of 38 μm using a blade coater, the coating film was dried at 100 ° C. for 3 minutes, and then the solvent was removed. A resist film having a thickness of 8 mu m was formed on the supporting film I.

(B) The inorganic powder-containing resin composition I prepared in Example 1 (1) was applied onto a support film II made of a PET film having a film thickness of 38 µm using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes. After removing the solvent, an inorganic powder-containing resin layer having a thickness of 10 μm was formed on the supporting film II.

(C) The transfer film was superposed so that the surface of the resist film and the inorganic powder containing resin layer could contact, and it was thermo-compressed with the heating roller. Here, as crimping | compression-bonding conditions, the surface temperature of the heating roller was 90 degreeC, the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. This produced the transfer film in which the laminated | multilayer film which has a resist film and an inorganic powder containing resin layer was formed between support films.

(3) Transfer process of laminated film:

The transfer film was superposed so that the surface of the inorganic powder containing resin layer of the transfer film manufactured by said (2) could contact the surface of a glass substrate, and this transfer film was thermocompression-bonded to the heating roller. Here, as crimping | compression-bonding conditions, the surface temperature of the heating roller was 90 degreeC, the roll pressure was 2.5 kg / cm, and the moving speed of the heating roller was 0.5 m / min. Thereby, the transfer film was transferred and adhered to the surface of the glass substrate.

(4) Exposure process and development process of resist film:

The resist film in the laminated film formed on the glass substrate in the above (3) is interposed with an exposure mask (100 µm wide stripe pattern and 5 cm square pattern) from the supporting film, and the g-line ( 436 nm), h-ray (405 nm) and i-ray (365 nm) were irradiated with mixed light. The exposure amount at that time was 400 mJ / cm 2 in terms of illuminance measured by a 365 nm sensor. After the irradiation, the support film on the resist film was peeled off, and the development process of the resist film by a shower method using 0.3 mass% aqueous sodium carbonate solution (30 ° C.) as a developer was performed for 90 seconds to the exposed resist film.

As a result, an uncured resist not irradiated with ultraviolet rays was removed to form a resist pattern. The resist pattern was uniform in pattern shape, excellent in linearity of the pattern edge, and good in shape.

(5) Etching Process of Inorganic Powder-Containing Resin Layer:

Subsequently to the above process, the etching process of the inorganic powder containing resin layer by the shower method which makes 0.3 mass% sodium carbonate aqueous solution (30 degreeC) an etching liquid was performed for 60 second.

Subsequently, water washing with ultrapure water and drying were performed. Thereby, the inorganic powder containing resin layer pattern was formed.

(6) firing process of the pattern:

The glass substrate in which the pattern of the inorganic powder containing resin layer was formed was baked at 580 degreeC for 30 minutes in the atmospheric atmosphere in a baking furnace. As a result, an electrode pattern having a thickness of 6 μm was formed on the surface of the glass substrate. The obtained electrode pattern had no cracks or defects and was excellent in shape.

Comparative Example 1

(a) 100 parts of Ag powder (average particle diameter: 2.2 µm) and glass frit (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system, average particle diameter of 3 µm, amorphous form, softening point 520 ° C, thermal expansion coefficient α ³⁰⁰ as inorganic powder = 87 × 10 ⁻⁷ / ° C.) 10 parts, (b) methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid-n-butyl = 10/35/60 (mass%) air 15.0 parts of coalescing (Mw = 50,000), (c) 0.5 parts of oleic acid as an acidic compound, (d) 10.0 parts of trimethylolpropanetriacrylate as a plasticizer, and (e) 100 parts of propylene glycol monomethyl ether as a solvent. Then, the inorganic powder containing resin composition (III) was manufactured by filtering by stainless mesh (500 mesh, 25 micrometer diameter).

The acid value of the inorganic powder-containing resin composition (III) was measured in the same manner as in Example 1 (2), and the acid value was 7.4 mgKOH / g.

Except having used the inorganic powder containing resin composition (III), the inorganic powder containing resin layer was formed like Example 1, the resist layer was formed on this inorganic powder containing resin layer, and the exposure process, image development, and the etching process were performed. The etching residue was recognized by the inorganic powder-containing resin layer, and a good pattern shape was not obtained. Moreover, when the development and etching process was extended in order to remove the said residue, the pattern of the inorganic powder containing resin layer peeled from the board | substrate before a residue disappeared.

Comparative Example 2

(a) Co ₃ O ₄ as inorganic powder 100 parts of powder (average particle diameter 0.4 µm) and glass frit (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system, average particle diameter 3 µm, indeterminate, softening point 520 ℃, coefficient of thermal expansion α ³⁰⁰ = 87 × 10 ^-7 / (Degree. C.) 10 parts, (b) methacrylic acid / methacrylic acid 2-hydroxypropyl / methacrylic acid-n-butyl = 30/30/40 (mass%) copolymer (Mw = 50,000) 120 (B) 20 parts of oleic acid as an acidic compound, (d) 20 parts of trimethylolpropanetriacrylate as a plasticizer, and (e) 100 parts of propylene glycol monomethyl ether as a solvent were kneaded with a bead mill, followed by stainless steel mesh (500). Inorganic powder-containing resin composition (IV) was prepared by filtering with a mesh).

When the acid value of the inorganic powder-containing resin composition (IV) was measured in the same manner as in Example 1 (2), the acid value was 105 mgKOH / g.

Except having used the inorganic powder containing resin composition (IV), the inorganic powder containing resin layer was formed like Example 1, the resist layer was formed on this inorganic powder containing resin layer, and the exposure process, image development, and the etching process were performed. All the inorganic powder-containing resin layers were dissolved to form a pattern. Moreover, when the time to perform the image development / etching process was shortened to 60 second, the pattern of the inorganic powder containing resin layer did not become square, the width | variety of the upper part of a pattern became very thin, and the favorable pattern shape was not obtained.

Comparative Example 3

A transfer film in which a resist film and an inorganic powder-containing resin layer were laminated was prepared in the same manner as in Example 3 except that the inorganic powder-containing resin composition (III) obtained in Comparative Example 1 was used as the inorganic powder-containing resin composition.

Using the obtained transfer film, transfer, exposure and development of the resist film, and etching of the inorganic powder-containing resin layer were carried out in the same manner as in Example 3, the etching residue was recognized in the inorganic powder-containing resin layer, and a good pattern shape was obtained. Not obtained. Moreover, when the development and etching process was extended in order to remove the said residue, the pattern of the inorganic powder containing resin layer peeled from the board | substrate before a residue disappeared.

The present invention controls the solubility of the inorganic powder-containing resin layer in the developing solution by adjusting the acid value of the inorganic powder-containing resin layer, so that the component of the PDP having excellent pattern shape (for example, dielectric layer, partition, electrode, resistor, phosphor, color) An inorganic powder-containing resin composition capable of preferably forming a filter, a black matrix) is provided.

This invention provides the transfer film which can form the component of PDP which is excellent in workability and excellent in pattern shape.

The present invention provides a method for producing a PDP that can form components of the PDP that are excellent in workability and excellent in pattern shape.

Claims (10)

(a) an inorganic powder, (b) binder resin, and (c) a low molecular weight compound having an acid value of 30 mgKOH / g or more, and having an acid value of 8 to 100 mgKOH / g measured by the method of JIS K 5601-2-1. Inorganic powder containing resin composition characterized by the above-mentioned. The inorganic powder containing resin composition of Claim 1 whose (b) binder resin is an acrylic resin containing a carboxyl group. The inorganic powder containing resin composition of Claim 1 whose (c) low molecular weight compound is an organic acid or an inorganic acid. The inorganic powder-containing resin composition according to claim 1, further comprising (d) a plasticizer. On the support film, (a) inorganic powder, (b) binder resin, and (c) the low molecular compound whose acid value is 30 mgKOH / g or more, and the acid value measured by the method of JISK5601-2-1 are 8-100. It has an inorganic powder containing resin layer which is mgKOH / g, The transfer film characterized by the above-mentioned. (A) resist layer, and (B) (a) inorganic powder, (b) binder resin, and (c) low molecular weight compound whose acid value is 30 mgKOH / g or more on a support film, Complies with JISK5601-2-1 The transfer film characterized by laminating | stacking the inorganic powder containing resin layer whose acid value measured by the method is 8-100 mgKOH / g. After forming the layer obtained from the inorganic powder containing resin composition of Claim 1 on a board | substrate, forming a resist layer on this layer, exposing this resist layer to form the latent image of a resist pattern, and developing this resist layer Processing the resist pattern to present the inorganic powder-containing resin layer, and etching the inorganic powder-containing resin layer to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern, and firing the pattern. The manufacturing method of the plasma display panel characterized by forming the panel material which has. The method for producing a plasma display panel according to claim 7, wherein the layer obtained from the inorganic powder-containing resin composition is formed by transferring the inorganic powder-containing resin layer onto the substrate using the transfer film according to claim 5. After forming the laminated film of the layer and resist layer obtained from the inorganic powder containing resin composition of Claim 1 on a board | substrate, exposing the said resist layer to form the latent image of a resist pattern, and developing the said resist layer and resist pattern Material of the inorganic pattern-containing resin layer by etching the inorganic powder-containing resin layer to form a pattern of the inorganic powder-containing resin layer corresponding to the resist pattern, and firing the pattern. Forming a plasma display panel, characterized in that for forming. The laminated film of the layer and resist layer obtained from an inorganic powder containing resin composition is formed by transferring the laminated film of an inorganic powder containing resin layer and a resist layer on a board | substrate using the transfer film of Claim 6. The manufacturing method of the plasma display panel.

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